CN113597372A - Composition for paper exterior coating and adhesive, and coated article, water-and oil-resistant paper laminate, paper straw, and paper tableware using the same - Google Patents

Composition for paper exterior coating and adhesive, and coated article, water-and oil-resistant paper laminate, paper straw, and paper tableware using the same Download PDF

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Publication number
CN113597372A
CN113597372A CN202080021948.9A CN202080021948A CN113597372A CN 113597372 A CN113597372 A CN 113597372A CN 202080021948 A CN202080021948 A CN 202080021948A CN 113597372 A CN113597372 A CN 113597372A
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China
Prior art keywords
paper
composition
meth
adhesive
acrylate
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CN202080021948.9A
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CN113597372B (en
Inventor
榎本肇
菊池�浩
越知卫
伊藤好树
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DIC Graphics Corp
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DIC Graphics Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • C09J125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/21—Paper; Textile fabrics
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Abstract

The present invention relates to a composition for paper coating and adhesive, which is characterized by containing an emulsion containing a resin containing a styrene-acrylic copolymer of styrene, alpha-methylstyrene and (meth) acrylate, and an aqueous medium, and a laminate such as a paper cup, a paper straw and the like, and a resin layer having the composition, wherein the emulsion has a minimum film-forming temperature in the range of-30 ℃ to 30 ℃. The present invention can combine the function of an adhesive for bonding a paper base material to a paper base material or a plastic film and the function of water resistance and oil resistance desired for an overcoat agent on the surface of the paper base material, and can reuse paper without distinction when paper is reused. Therefore, the composition for overcoating and adhesive of the present invention is used as a substitute for polyethylene in paper containers and the like.

Description

Composition for paper exterior coating and adhesive, and coated article, water-and oil-resistant paper laminate, paper straw, and paper tableware using the same
Technical Field
The present invention relates to a composition for paper overcoating and an adhesive, which imparts water resistance, oil resistance, and oil repellency to paper and has an adhesive function.
Background
A packaging material for cooked food such as snack food or side food such as donuts, hamburgers and the like is required to have water resistance or oil resistance so that moisture or oil of the contents does not permeate, and further, to have appropriate moisture permeability so that the contents are not wetted by water vapor generated from the food to impair the flavor when heated in a microwave oven. As a method for imparting such a function to paper as a packaging material, a method of coating a composition using a fluorine-based compound such as acrylate or phosphate of perfluorocarbon has been conventionally performed. However, the fluorine-based composition is pointed out as follows: when heating is performed, fluorine-containing compounds present in the paper are thermally decomposed to generate "hardly decomposable" fluorine-containing hydrocarbons in nature, which causes environmental pollution and the like.
On the other hand, for example, in patent document 1, an oil-resistant paper having excellent oil resistance and air permeability is produced by providing a coating layer of cellulose nanofibers having carboxyl groups on a paper substrate. However, the cellulose nanofibers obtained by the production method of patent document 1 are likely to be swollen and disintegrated by water because the carboxyl groups on the surface of the crystalline cellulose nanofibers are in a salt form. Many subsidiary foods and snack foods contain a large amount of moisture in addition to oil, and the coating layer of cellulose nanofibers is disintegrated by the moisture in the contents, which may cause contamination of the contents and permeation of moisture and oil. Therefore, a coating agent having water resistance, oil resistance and high safety is required.
In recent years, in the process of paying attention to the problem of marine plastic waste including micro plastic, attention is being given to "paper" made of "wood" as a renewable resource as one of raw materials having functions such as "recyclable" and "biodegradable".
Paper cups, which are one of paper containers for food, which are widely used at present, are made of paper, but a polyethylene film, which reduces recycling efficiency, is used as a part of raw materials. Generally, a paper cup is obtained by laminating a polyethylene film, a polypropylene film, or the like obtained by extruding a polyethylene resin, a polypropylene resin, or the like melted by heat into a film shape to a paper base. In the case of forming a paper cup, the polyethylene film functions as an adhesive by heat fusion under indirect heating with a burner, hot air, or the like, and the polyethylene film is present inside the paper cup, so that the paper base does not come into direct contact with the contents and is provided with water repellency and strength.
However, the polyethylene film to be bonded does not dissolve in the alkaline solution used for the paper recycling process at the time of paper recycling, and therefore, it needs to be physically removed, which leads to a decrease in recycling efficiency. In addition, marine pollution caused by the outflow of plastic waste to the ocean is a worldwide problem. The sustainable development targets (SDGs) aim to prevent and greatly reduce all kinds of marine pollution, especially pollution caused by land activities including marine waste and eutrophication, etc. by 2025, and the first-brain conference (the leading meeting of the major countries) also agrees to reinforcement measures, and the reduction of plastic waste becomes an important issue worldwide. Therefore, there is a need for a polyethylene film alternative that can be applied to these uses without reducing the paper recycling efficiency. In addition, a paper container that does not use a plastic film is required.
Regarding paper straws, a turtle who discovered that the nose was punctured by a straw in the area of dawn rica in south america in 2015 is attracting much attention because the exercise of eliminating the use of plastic straws is rapidly spreading throughout the world, and the american large hamburger chain is planned to eliminate the use of plastic straws in some european markets in stages and introduce paper straws instead.
Furthermore, the british government has announced in 2018 that the sale of disposable plastic drinking straws will be prohibited, and at the same time, the European Union (EU) has also proposed measures to prohibit plastic drinking straws. In addition, the indian government expressed that disposable plastic articles were banned before 2022, and the impact on asian areas is also becoming increasingly realistic.
Under such circumstances, some catering industry in japan has gradually accelerated the shift to paper straws.
On the other hand, since a paper straw is produced by laminating 2 or more thin paper sheets, smoothness in the lamination and water resistance accompanying water supply when the straw is used are required, and in the case of a paper straw using a paper laminate using a polyvinyl alcohol-based adhesive or a starch-based adhesive which has been conventionally used, water resistance is particularly insufficient, and strength as in the case of a plastic straw cannot be maintained.
On the other hand, for example, patent document 2 discloses an invention of an aqueous paper adhesive in which an aqueous dispersion of a specific polyolefin resin and an organic amine compound are blended at a specific ratio in order to improve adhesion to paper, but the aqueous paper adhesive is not sufficient in smoothness and water resistance at the time of bonding, and is insufficient in strength as a laminate for paper tableware.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-74535
Patent document 2: japanese patent laid-open publication No. 2003-213233
Disclosure of Invention
The present invention addresses the problem of providing an overcoat composition for paper, which does not contain a fluorine-based compound and imparts water resistance, oil resistance, and oil repellency to paper by coating alone. Further, another object of the present invention is to provide a composition for paper overcoating and an adhesive, which has both a function as an adhesive for bonding a paper base material to a paper base material or a plastic film, which is desired as a substitute for a paper container such as a paper cup, a polyethylene film used for a paper straw, and the like, and a function as a water resistance and an oil resistance which are desired as an overcoating agent on the surface of a paper base material, and which can be reused indiscriminately when paper is reused, and a coated article, a water-and oil-resistant paper laminate, a paper straw, and a paper tableware using the same.
That is, the present invention relates to a composition for paper overcoating and adhesive, comprising an emulsion containing a styrene-acrylic copolymer of styrene, α -methylstyrene and a (meth) acrylate, and an aqueous medium, wherein the emulsion has a minimum film-forming temperature in the range of-30 ℃ to 30 ℃.
Since the paper coating and adhesive composition of the present invention does not contain a fluorine-containing compound, it does not generate "hardly decomposable" fluorine-containing hydrocarbons even when heated. Further, since paper can be imparted with good water resistance, oil resistance and oil repellency only by coating, a coated product obtained by applying the composition for paper exterior coating and adhesive of the present invention to paper can be safely used for food packaging materials, containers, straws and the like. Further, the paper coating and adhesive composition of the present invention also has a function as an adhesive, and therefore, can have both a function as an adhesive for bonding a paper base to a paper base or a plastic film, which is desired as a substitute for a paper container such as a paper cup or a polyethylene film used for a paper straw, and a function as a water resistance and an oil resistance which are desired as an external coating agent on the surface of a paper base, and can be reused indiscriminately when paper is reused. Therefore, the composition for overcoating and adhesive of the present invention is used as a substitute for polyethylene in paper containers and the like.
Detailed Description
(emulsion)
The emulsion used in the present invention contains a resin of a styrene-acrylic copolymer containing at least styrene, alpha-methylstyrene and a (meth) acrylic ester, and has a minimum film-forming temperature in the range of-30 ℃ to 30 ℃.
The paper overcoat composition using the emulsion of the present invention has a dense film-forming property without defects such as pinholes, and is therefore excellent in water resistance and oil resistance. Further, the emulsion of the present invention has adhesiveness, and therefore, can be used as an adhesive composition for bonding paper or paper to a film.
(styrene-acrylic copolymer of styrene, alpha-methylstyrene and (meth) acrylate)
The styrene-acrylic copolymer of styrene, α -methylstyrene and (meth) acrylic acid ester (hereinafter sometimes referred to as styrene-acrylic copolymer (a)) used in the present invention is a copolymer of styrene, α -methylstyrene and (meth) acrylic acid ester.
In the present invention, (meth) acrylate represents a generic name of acrylate and methacrylate, and (meth) acrylic acid represents a generic name of acrylic acid and methacrylic acid.
In the present invention, α -methylstyrene represents any one or a mixture of o-methylstyrene, m-methylstyrene, p-methylstyrene. Since the composition of the present invention contains the styrene-acrylic copolymer (a), heat resistance is improved.
In addition, a part of styrene derivatives other than the above styrene and the above α -methylstyrene (p-dimethylsilylstyrene, p-tert-butyldimethylsilyloxystyrene, p-tert-butylstyrene), vinylnaphthalene, vinylanthracene, 1-diphenylethylene, and the like may be used within a range not to impair the scope of the present invention.
The (meth) acrylic acid ester is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, allyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, n-tridecyl (meth) acrylate, n-stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and mixtures thereof, Tricyclodecyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, pentafluoropropyl methacrylate, octafluoropentyl methacrylate, pentadecafluorooctyl methacrylate, heptadecafluorodecyl methacrylate, N-dimethyl (meth) acrylamide, acryloylmorpholine, (meth) acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, propylene glycol-propylene glycol (meth) acrylate, propylene glycol-propylene glycol (meth) acrylate, and the like, General-purpose (meth) acrylates such as polyalkylene oxide group-containing (meth) acrylic acid monomers including polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, lauryloxypolyethylene glycol (meth) acrylate, stearyloxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate. Among them, the homopolymer having an acrylic ester has a lower glass transition temperature, and therefore, it is preferable to use an acrylic ester having an alkyl group having 1 to 20 carbon atoms as a main component, and to use an acrylic ester having an alkyl group having 1 to 12 carbon atoms as a main component. Examples of the acrylic ester having an alkyl group having 1 to 12 carbon atoms include methyl acrylate, ethyl acrylate, isopropyl acrylate, allyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl (meth) acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and n-lauryl (meth) acrylate. The (meth) acrylic acid ester used as a constituent component of the styrene-acrylic copolymer (a) of the present invention may be 1 kind, or 2 or more kinds, and preferably 2 or more kinds of (meth) acrylic acid esters are used, and among them, 2 or more kinds of acrylic acid esters having an alkyl group having 1 to 12 carbon atoms are preferably used as a main component.
The emulsion used in the present invention preferably further contains a copolymer of (meth) acrylic acid and (meth) acrylic acid ester. The copolymer of (meth) acrylic acid and (meth) acrylic acid ester is a copolymer of (meth) acrylic acid and the above (meth) acrylic acid ester (hereinafter, may be referred to as an acrylic copolymer (B)). The (meth) acrylate is not particularly limited, but among them, an acrylate having an alkyl group having 1 to 20 carbon atoms is preferable, and since a homopolymer having an acrylate exhibits a lower glass transition temperature, an acrylate having an alkyl group having 1 to 20 carbon atoms is preferable as a main component, and an acrylate having an alkyl group having 1 to 12 carbon atoms is preferable as a main component. Examples of the acrylic ester having an alkyl group having 1 to 12 carbon atoms include methyl acrylate, ethyl acrylate, isopropyl acrylate, allyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl (meth) acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and n-lauryl (meth) acrylate.
The emulsion used in the present invention preferably contains the styrene-acrylic copolymer (a) and the acrylic copolymer (B), and may be an emulsion obtained by appropriately mixing an emulsion of the styrene-acrylic copolymer (a) polymerized by a polymerization method using a known aqueous medium such as emulsion polymerization or transfer emulsification and an emulsion of the acrylic copolymer (B) polymerized by a polymerization method using a known aqueous medium such as emulsion polymerization or transfer emulsification, or may be an emulsion in which the styrene-acrylic copolymer (a) and the acrylic copolymer (B) form a resin having a core-shell structure. The "resin containing the styrene-acrylic copolymer (a)" may be a resin formed from the styrene-acrylic copolymer (a), or may be a resin in which the styrene-acrylic copolymer (a) and the acrylic copolymer (B) form a core-shell structure.
(method for producing emulsion)
In the present invention, the emulsion is not particularly limited, and can be obtained by polymerization using a known aqueous medium, such as known emulsion polymerization or transfer emulsification. The form in which the polymer is dispersed in the aqueous medium may be an emulsion, a dispersion, a suspension, or the like, but is generally an emulsion in the present invention.
For example, a monomer mixture is supplied in an aqueous medium, and the monomer mixture is polymerized in the presence of an initiator to polymerize an emulsion.
In the case of an emulsion obtained by appropriately mixing the emulsion of the styrene-acrylic copolymer (a) and the emulsion of the acrylic copolymer (B), the emulsion can be obtained by mixing emulsions obtained by polymerizing respective monomer mixtures.
In addition, in the case of forming an emulsion having a core-shell structure, the emulsion is obtained by the steps (1) and (2), wherein in the step (1), a monomer mixture for forming a core polymer is supplied, and the monomer mixture is polymerized in the presence of an initiator to form a core polymer, and in the step (2), a monomer mixture for forming a shell polymer is supplied to the core polymer in the step (1), and the monomer mixture is polymerized in the presence of an initiator to form a shell in the core polymer. The core polymer is obtained by the steps (i) and (ii), in which in the step (i), a monomer mixture for forming the shell polymer is supplied, and the monomer mixture is polymerized in the presence of an initiator to form the shell polymer, and in the step (ii), a monomer mixture for forming the core polymer is supplied to the shell polymer in the step (i), and the monomer mixture is polymerized in the presence of an initiator to form the shell in the core polymer.
The initiator is not particularly limited, and a peroxide, persulfate, azo compound, redox system, or mixture thereof used in emulsion polymerization or the like may be used. Examples of the peroxide include hydrogen peroxide, ammonium peroxide, sodium peroxide or potassium peroxide, t-butyl hydroperoxide, cumene hydroperoxide and benzene peroxide. Examples of the persulfate include ammonium persulfate, sodium persulfate, and potassium persulfate. Examples of the azo compound include 2, 2-azobisisobutyronitrile and 4, 4' - (4-cyanovaleric acid). The redox system is composed of an oxidizing agent and a reducing agent, and examples of the oxidizing agent include the 1 types of peroxides, persulfates, azo compounds, sodium chloride or potassium chloride, or sodium bromide or potassium bromide mentioned above. Examples of the reducing agent include ascorbic acid, glucose, or ammonium, sodium hydrogen sulfate or potassium hydrogen sulfate, sodium hydrogen sulfite or potassium hydrogen sulfite, sodium thiosulfate or potassium thiosulfate, or sodium sulfide or potassium sulfide, or ammonium iron (II) sulfate.
Among them, a persulfate is preferable, and ammonium persulfate is more preferable.
The polymerization of the above monomer mixture may be carried out in the presence of an additive such as a surfactant, a chain transfer agent, a chelating agent, etc., for example, in the presence of a surfactant and a chain transfer agent. These additives may be added to the aqueous medium used in step (1) in advance, or may be mixed with the monomer mixture supplied in step (1) or step (2).
The surfactant is not particularly limited, and examples thereof include disodium dodecyl diphenyl oxide and disulfonate. The chain transfer agent is also not particularly limited, and examples thereof include α -methylstyrene dimer, thioglycolic acid, sodium hydrogen phosphite, 2-mercaptoethanol, N-dodecylmercaptan, and t-dodecylmercaptan. The chelating agent is not particularly limited, and for example, ethylenediaminetetraacetic acid is given.
In the case of forming a core-shell structure, it is preferable that the acrylic copolymer (B) having an acidic group is a shell in order to improve stability in an aqueous medium, but even an emulsion having a structure in which not all of the acrylic copolymer (B) is a shell but a part of the styrene acrylic copolymer (a) is a shell during synthesis has no problem.
When neutralization is required, bases such as ammonia, triethylamine, aminomethylpropanol, monoethanolamine, diethylaminoethanol, sodium hydroxide, and potassium hydroxide can be used as the neutralizing agent.
(minimum film Forming temperature)
The lowest film forming temperature of the emulsion is in the range of-30 ℃ to 30 ℃.
In the present invention, the minimum film-forming temperature is the minimum temperature required for forming a continuous film upon evaporation drying of the water content of the synthetic rubber latex, and is obtained by the temperature gradient plate method. Among them, the temperature is preferably in the range of-10 to 25 ℃, and more preferably in the range of-5 to 20 ℃.
The glass transition temperature (hereinafter, sometimes referred to as Tg) of the emulsion is preferably in the range of-40 to 30 ℃, more preferably in the range of-35 to 25 ℃, and still more preferably in the range of-30 to 23 ℃.
In the present invention, the glass transition temperature is obtained by measurement using a differential scanning calorimeter.
The acid value of the emulsion is preferably in the range of 30 to 80mgKOH/g, more preferably 40 to 75mgKOH/g, and still more preferably 50 to 70 mgKOH/g.
In the present invention, the acid value is obtained by the measurement method according to K0070-1992.
(other resins)
The paper overcoat composition of the present invention may contain a resin other than the styrene-acrylic copolymer (a) and the acrylic copolymer (B).
For example, the paper top coating composition of the present invention preferably further contains a resin having a glass transition temperature higher than that of the resin containing the styrene-acrylic copolymer (a) (hereinafter, may be referred to as a resin (C) having a high glass transition temperature). By containing such a resin (C) having a high glass transition temperature, the blocking resistance can be improved, and the slip property when the coated papers coated with the coating composition of the present invention are laminated can be improved. The glass transition temperature of the resin (C) is preferably higher by 20 ℃ or more, more preferably higher by 30 ℃ or more than the glass transition temperature of the resin containing the styrene-acrylic copolymer (A). In addition, the glass transition temperature of the resin (C) is preferably in the range of 0 to 85 ℃ so as not to impair the effects of the coating composition of the present invention. Specifically, the glass transition temperature of the resin containing the styrene-acrylic copolymer (A) is preferably in the range of-40 ℃ to 0 ℃, and the glass transition temperature of the resin (C) is preferably in the range of 0 ℃ to 40 ℃.
The material of the resin (C) having a high glass transition temperature is not particularly limited, and a styrene-acrylic copolymer is preferable, and the same material as the resin containing the styrene-acrylic copolymer (a) is more preferable, so as not to impair the properties of the coating composition of the present invention, such as oil resistance and heat resistance. The content of the resin (C) may be appropriately adjusted depending on the desired blocking resistance and stacking property, and the weight ratio of the resin containing the styrene-acrylic copolymer (A) to the resin (C) (styrene-acrylic copolymer (A)/resin (C)) is preferably 90/10 to 20/80, and preferably 80/20 to 30/70.
The emulsion used in the present invention containing the resin (C) having a high glass transition temperature can be obtained by, for example, appropriately mixing an emulsion containing a resin containing the styrene-acrylic copolymer (a) with an emulsion of the resin (C) obtained by polymerization using a known aqueous medium such as emulsion polymerization or transfer emulsification.
(other additives)
The paper topcoat composition of the present invention may further contain other silica, alumina, polyethylene wax, a defoaming agent, a leveling agent, a thickener, a preservative, an antibacterial agent, a rust preventive, and the like.
The emulsion used in the present invention contains wax, and therefore, can improve workability because the slip property when coated papers coated with the coating composition of the present invention are laminated is good. Examples of the wax include fatty acid amide wax, carnauba wax, polyolefin wax, paraffin wax, fischer-tropsch wax, beeswax, microcrystalline wax, oxidized polyethylene wax, and amide wax. They may be used alone or in combination.
Among them, fatty acid amide wax, carnauba wax, fischer-tropsch wax, polyolefin wax, and paraffin wax are preferably used, and particularly carnauba wax, polyolefin wax, and paraffin wax are preferably used.
Specific examples of the fatty acid amide wax include nonanoic acid amide, decanoic acid amide, undecanoic acid amide, lauric acid amide, tridecanoic acid amide, myristic acid amide, pentadecanoic acid amide, palmitic acid amide, heptadecanoic acid amide, stearic acid amide, nonadecanoic acid amide, arachic acid amide, behenic acid amide, lignoceric acid amide, oleic acid amide, cetenoic acid amide, linoleic acid amide, linolenic acid amide, mixtures thereof, and animal and vegetable fat fatty acid amides.
Specific examples of the carnauba wax include MICROKLEAR418(Micro Powders, Inc.), purified carnauba wax No. 1 powder (Japan wax Co., Ltd.), and the like.
Specific examples of the olefin wax include polyethylene wax and polypropylene wax, and examples thereof include MPP-635VF (MicroPowders, Inc.), MP-620VFXF (MicroPowders, Inc.), and the like.
Specific examples of the paraffin include MP-28C, MP-22XF and MP-28C (MicroPowders, Inc.).
The amount of the wax blended is preferably 1.5 to 20% by mass of the total amount of the wax based on 100% by mass of the solid content in the composition of the present invention. If the total amount of wax is 3% by mass or more based on 100% by mass of the total solid content in the composition of the present invention, blocking resistance tends to be maintained, and if the total amount of wax is 15% by mass or less based on 100% by mass of the total solid content of the aqueous heat-sealing agent, heat sealability tends to be maintained.
The melting point of the wax is preferably in the range of 80 to 130 ℃.
The wax may be added directly to the emulsion of the resin containing the styrene-acrylic copolymer (a) and mixed and dispersed, or may be mixed with the emulsion after the wax dispersion is prepared. As the dispersion method, a known method can be used, and for example, as a dispersion apparatus using a medium, a paint shaker, a ball MILL, an attritor, a basket MILL, a sand MILL, a DYNO-MILL, a DISPERMAT, an SC MILL, a pin MILL, a stirring MILL, or the like can be used, and as a dispersion apparatus not using a medium, dispersion can be performed by an ultrasonic homogenizer, a high-pressure homogenizer, a Nanomizer, a dissolver, a disperser, a high-speed impeller disperser, or the like.
When a wax powder is used, it is preferable to knead the wax using a medium or blend the wax powder after preparing a wax dispersion in order to uniformly disperse the wax. The kneading method can be carried out by a known method.
When a plurality of types of waxes are used in combination, the plurality of types of waxes may be added simultaneously or may be added in a plurality of steps.
In the paper coating and adhesive composition of the present invention, it is preferable to use a polymer-based defoaming agent, a silicon-based defoaming agent, or a fluorine-based defoaming agent in order to prevent foaming of the composition when the composition is applied by using various coating machines. As these defoaming agents, emulsion dispersion type, solubilized type, and the like can be used. Among them, a polymer-based defoaming agent is preferable.
The amount of the defoaming agent added is preferably 0.005 to 0.1% by weight based on the total amount of the paper top coating composition.
As a specific example of the composition for paper overcoating and adhesive of the present invention, as a coating method, for example, a roll coater, a gravure coater, a flexographic coater, an air knife coater, a knife coater, an air knife coater, a squeeze coater, an impregnation coater, a transfer roll coater, a kiss coater, a curtain coater, a casting coater, a spray coater, a die coater, an offset printer, a screen printer, and the like can be suitably used, and the obtained printed matter is post-processed according to various uses and used for packaging of commercial products such as food.
(coating step of coating the paper base with the external coating composition)
The paper substrate used in the present invention is produced by using natural fibers for papermaking such as wood pulp and using a known papermaking machine, but the papermaking conditions are not particularly limited. Examples of the natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, nonwood pulp such as manila pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps. As the kind of pulp, chemical pulp, ground pulp, chemically ground pulp, thermomechanical pulp, and the like by a sulfate digestion method, an acid, neutral, and alkaline sulfite digestion method, a sodium salt digestion method, and the like can be used.
Further, various commercially available high-quality papers, coated papers, lining papers, impregnated papers, yellow papers, and cardboard can be used.
As a method for applying the dispersion of the present invention to a paper substrate, any one or two or more coating methods of a comma coater, a roll coater, a reverse roll coater, a direct gravure coater, a reverse gravure coater, an offset gravure coater, a roll kiss coater, a reverse kiss coater, a kiss gravure coater, a reverse kiss gravure coater, an air knife coater, a bar coater, a wire bar coater, a die coater, a lip coater, a dip coater, a blade coater, a brush coater, a curtain coater, a die gap coater, and the like may be used in combination.
Further, the paper substrate may be impregnated with the paper coating and adhesive composition of the present invention to provide a resin layer on the paper substrate.
The film thickness of the paper topcoat and adhesive composition of the present invention at the time of coating varies depending on the application, but when used for a food paper container, the film thickness is, for example, 2 to 10g/m2The effects of the present invention can be sufficiently obtained within the range of (1). Among them, more preferably 6 to 10g/m2The range of (1).
Since the coated product obtained by coating the paper topcoat and adhesive composition of the present invention on a paper substrate has water resistance, oil resistance, and oil repellency, the coated product can be used as water-resistant paper and/or oil-resistant paper when used as a paper topcoat. The coating material of the present invention is widely used for paper cups, noodles in cups, various beverages, desserts such as ice cream, pudding, and jelly, rice snacks, potato chips, chocolate snacks, snack snacks such as cookies, hamburgers, hot dog wrap, take-away containers such as pizza, dry fried foods, snack containers such as potatoes, paper containers for foods represented by cups containing home vegetables such as natto, and straws.
(method of manufacturing paper Container)
As a specific embodiment of producing a paper container using the composition for paper overcoating and adhesive of the present invention, a method for producing a paper cup-shaped paper container using a laminate in which at least a paper base and a paper base or a plastic film are bonded to each other, the laminate having a resin layer of the composition for paper overcoating and adhesive of the present invention on at least one surface of the paper base, will be specifically described. In the present specification, the term "laminate" refers to a portion in which at least a part of paper and paper or a part of paper and a plastic film overlap each other. The present invention is not limited to the specific embodiment, and can be applied to all paper containers that can be coated.
A paper cup using the laminate of the present invention comprises a main body member (1) and a plate-like bottom member (2), wherein the main body member (1) is formed by laminating and bonding surfaces at both rolled and overlapped end portions of a paper base material, and the bottom member (2) is bonded to the lower end of the main body member (1). The paper cup is provided with a resin layer on the inner surface of the container and the contact surface when the container is assembled, and the composition for paper coating and adhesive of the present invention is used for the resin layer.
The tubular main body member (1) and the plate-like bottom member (2) are each obtained by cutting a paper base provided with a resin layer into a desired shape.
First, the paper base material is coated with the paper top coating and adhesive composition of the present invention on at least a part of the inner surface (inner surface of the projection) of the paper container and/or the surface to be the contact surface. As the coating method, the above-described coating method can be suitably used. After the coating, the aqueous solvent on the coated surface is removed by a dryer or the like, and then printing is performed as necessary. The printing surface is often applied to the surface opposite to the coated surface.
Next, in a paper substrate provided with a resin layer by coating, the cylindrical body member (1) is cut into a fan shape, and the plate-like base member (2) is cut into a circular shape. The order of the step of providing the resin layer on the paper base and the step of cutting the paper base is not particularly limited, and the resin layer may be provided after the paper base is cut into a fan-shaped or circular shape.
After the composition of the present invention is applied to a paper substrate, the bonding surfaces at both ends of the body member (1) cut into a fan-like cylindrical shape are overlapped in a dry state where the composition has adhesiveness and adhesiveness, and pressure bonding or thermocompression bonding is performed. The method of thermocompression bonding is not particularly limited, and a heat source such as a burner or hot air may be used. The order of heating, overlapping, and pressure bonding is not particularly limited, and when the bonding surfaces are overlapped with each other and pressure bonded while heating with a heat source, drying of the composition applied by heating does not proceed, and thus the composition can be more firmly bonded without impairing the adhesiveness, which is preferable. The heating temperature is preferably 200 to 450 ℃ and the heating and pressing time is preferably 0.5 to 3 seconds.
On the other hand, the circularly cut bottom member (2) is provided inside the cylindrical main body member so that the surface coated with the composition of the present invention is inside the cup, and then the resin layers on the bottom member side and the main body member side are bonded by pressure bonding or thermocompression bonding in the same manner as described above, thereby bonding the bottom member to the contact portion of the main body member. In this case, the resin layer fills the gap between the base member and the body member, so that water leakage or the like does not occur.
Then, the aqueous solvent of the resin layer on the inner surface of the paper container may be removed by a dryer or the like.
In the production of the paper cup, the paper cup can be obtained by a known process, for example, a method in which the lower end of the bottom side of the body member is folded inward, and the bottom of the paper cup is pressed by a rotating circular die to finish the bottom. Finally, a portion of the upper end of the body member corresponding to the drinking opening is subjected to a forming process called curling, in which the tool is rolled into the outer side of the paper cup while being rotated, as necessary.
The paper container of the above-described specific embodiment is mainly a cup-shaped container having a disk-shaped bottom member, but the shape is not limited to this, and may be, for example, a rectangular parallelepiped, polygonal, or cubic container having a rectangular plate-shaped bottom member. Further, if necessary, the container may be sealed with a separately manufactured lid material or the like, and the lid material may be removed or a part of the container may be opened for use when heating in a microwave oven or the like, for example.
By the above-described operation, a laminate (paper container) in which a paper base and a paper base are bonded to each other through a resin layer of the composition of the present invention can be obtained, and a laminate (paper container) having a resin layer for external coating in a portion where the paper base and the paper base are not laminated can be obtained.
In the above method, the structure in which the resin layer of the composition of the present invention is provided on both the portion to be the inner surface (inner surface of the projection) of the paper container and/or the surface to be the bonded surface has been described, but for example, the structure in which only the resin layer for external coating is provided on the inner surface of the paper container, and other adhesive materials such as a heat-sealing agent are provided on the bonded surface to bond them, or the structure in which the resin layer of the present invention is used as an adhesive only on the bonded surface may be employed.
(method of manufacturing paper straw)
Next, a method for manufacturing a paper drinking straw using the laminate of the present invention will be specifically described. The paper straw of the present invention has a cylindrical structure in which at least one end of 1 or more sheets of paper are laminated. The paper straw is provided with a resin layer on the surface (inner surface and outer surface) of the straw and the laminated bonding surface, and the composition for paper coating and adhesive of the present invention is used as the resin layer.
The paper straw may be formed by winding 1 sheet of paper into a cylindrical shape and bonding the ends of the paper, or may be formed into a cylindrical shape by winding a plurality of sheets of paper in a band shape into a spiral shape and bonding the sheets of paper to each other. Hereinafter, a method of manufacturing the spiral straw will be described.
First, a strip-shaped paper substrate is prepared, and resin layers of the composition of the present invention are provided on both sides of the paper substrate. As a method for forming the resin layer, the above-described coating method or impregnation method can be suitably used. In addition, a sheet-like paper substrate may be prepared, and a resin layer of the composition of the present invention may be provided thereon, and then cut to form a tape-like paper substrate. In view of the water resistance and strength of the paper straw, it is preferable to use 2 or 3 strip paper substrates as the paper substrate, and when a plurality of strip-shaped rolls are wound in a spiral shape, the type of the paper substrate can be changed between the paper positioned inside the straw and the paper positioned outside the straw. For example, the inner paper may be relatively thick for providing strength, and the outermost paper may be relatively thin for smoothing the surface, and printing may be performed as necessary. The width of the band can be adjusted as appropriate depending on the desired diameter (width) of the straw, and is preferably about 0.5cm to 2.0cm, for example.
After the composition of the present invention is applied to a paper substrate, a strip of paper is spirally wound around a core member in a dry state in which the composition has adhesiveness and tackiness. At this time, the ends of the previously wound sheets are overlapped, and at the same time, for example, 3 sheets of the tape positioned on the innermost side of the straw, the tape positioned in the middle, and the tape positioned on the surface are sequentially wound, and the bonding surfaces of the tape-shaped sheets are pressure-bonded or thermocompression-bonded. The above-mentioned method of using a heat source and heating temperature for thermocompression bonding can be appropriately employed.
Then, the water-based solvent of the resin layer on the inner surface and the surface of the paper straw is removed by a dryer or the like, and the core member is extracted, thereby forming a hollow cylindrical straw.
By the above-described operation, a laminate (a paper straw) in which a paper base and a paper base are bonded to each other through the resin layer of the composition of the present invention can be obtained, and a laminate (a paper straw) having a resin layer for external coating in a portion where the paper base and the paper base are not laminated can be obtained.
In the above method, an example in which a paper base and a paper base are laminated was described, but the paper base and a plastic film may be bonded or the surface may be coated with the composition of the present invention. For example, in a paper straw, a laminate in which a strip-shaped paper and a strip-shaped film are laminated may be used as the straw.
The present invention will be described in detail below with reference to examples, but the technical scope of the present invention is not limited to these embodiments.
The minimum film formation temperature was measured using a film formation temperature tester (manufactured by Kokusho Kogyo Co., Ltd.) by a temperature gradient plate method.
The glass transition temperature (Tg) was measured as follows: scanning was performed using a differential scanning calorimeter ("DSCQ 100" manufactured by TA Instruments, Inc.) under a nitrogen atmosphere at a temperature range of-80 to 450 ℃ and a temperature rise of 10 ℃/min using a cooling apparatus.
The acid value was measured in accordance with JIS test method K0070-. The amount of the polymer was determined by dissolving 0.5g of the polymer in a Tetrahydrofuran (THF) solvent, and titrating the solution with 0.1M alcoholic potassium hydroxide solution using phenolphthalein as an indicator.
[ examples ] A method for producing a compound
Production example 1
< Synthesis of acrylic emulsion >
First, the core/shell type acrylic emulsion used in example 1 was synthesized. In the synthesis examples, "part" means "part by weight" and "%" means "% by weight".
(Synthesis example 1)
100 parts of isopropyl alcohol was put into a four-necked flask purged with nitrogen, the temperature was raised to 80 to 82 ℃, and then a mixture of 1 part of myristyl acrylate, 30 parts of styrene, 10 parts of acrylic acid, 5 parts of methyl methacrylate, and 1 part of benzoyl peroxide, which was put into a dropping funnel, was dropped over 2 hours. After completion of the dropwise addition, 0.5 part of benzoyl peroxide was added thereto, and the reaction was further continued for 2 hours. The temperature was lowered to 40 ℃ and dimethylethanolamine and ion-exchanged water were added. Then, the temperature of the reaction flask is raised to 80-82 ℃, and steam stripping is carried out, so that the water-soluble resin with the solid content of 30% is finally obtained.
To the water-soluble resin obtained above, 10 parts of ion-exchanged water was put into a reaction flask, the temperature was raised to 80 to 82 ℃, 2 parts of potassium persulfate was added, and a mixture of 15 parts of styrene, 5 parts of α -methylstyrene, 24 parts of 2-ethylhexyl acrylate and 10 parts of butyl acrylate was added dropwise over 2 hours. After completion of the dropwise addition, 0.2 part of potassium persulfate was added and allowed to react for 2 hours. The acrylic emulsion (resin 1) thus obtained had a solid content of 40%, a minimum film-forming temperature of 1 ℃, a glass transition temperature of-27 ℃ and an acid value of the solid content of 64 mgKOH/g.
(example 1)
A total of 100 parts of 85 parts of the acrylic emulsion (resin 1), 0.03 part of a polymer defoaming agent and 14.97 parts of ion-exchanged water was sufficiently stirred at 25 ℃ for 15 minutes by a dispersing device to prepare an overcoat composition for paper.
(example 2)
An overcoat composition for paper was prepared in the same procedure as in example 1 except that 85 parts of a commercially available acrylic emulsion a having a "styrene-acrylic copolymer of styrene, α -methylstyrene and (meth) acrylic ester (styrene-acrylic copolymer (a))" was used instead of the acrylic emulsion (resin 1) of example 1.
The commercially available acrylic emulsion A had a minimum film-forming temperature of 18 ℃ and a glass transition temperature of 21 ℃ and an acid value of the solid content of 55 mgKOH/g.
(example 3)
An overcoat composition for paper was prepared in the same manner as in example 1 except that 85 parts of a commercially available acrylic emulsion B having a styrene-acrylic copolymer (a)) "of styrene, α -methylstyrene and (meth) acrylic ester was used in place of the acrylic emulsion (resin 1) of example 1.
The commercially available acrylic emulsion B had a minimum film-forming temperature of 1 ℃, a glass transition temperature of-9 ℃ and an acid value of the solid content of 61 mgKOH/g.
(example 4)
An overcoat composition for paper was prepared in the same manner as in example 1 except that 85 parts of a commercially available acrylic emulsion D having a styrene-acrylic copolymer of styrene, α -methylstyrene and a (meth) acrylic ester (styrene-acrylic copolymer (a)) "was used in place of the acrylic emulsion (resin 1) of example 1.
The commercially available acrylic emulsion D had a minimum film-forming temperature of 6 ℃, a glass transition temperature of 8 ℃ and an acid value of the solid content of 55 mgKOH/g.
(example 5)
An overcoat composition for paper was prepared in the same manner as in example 1 except that 64 parts of the acrylic emulsion (resin 1) of example 1 and 22 parts of the acrylic emulsion a of example 2 were mixed to prepare an acrylic emulsion (86 parts in total), and that 13.97 parts of ion-exchanged water was used.
(example 6)
An overcoat composition for paper was prepared in the same manner as in example 5 except that 43 parts of the acrylic emulsion (resin 1) of example 1 and 43 parts of the acrylic emulsion a of example 2 were mixed to prepare an acrylic emulsion (total of 86 parts).
(example 7)
An overcoat composition for paper was prepared in the same manner as in example 5 except that 21 parts of the acrylic emulsion (resin 1) of example 1 and 65 parts of the acrylic emulsion a of example 2 were mixed to prepare an acrylic emulsion (total of 86 parts).
(example 8)
To the acrylic emulsion of example 7 was added 1.2 parts of carnauba wax (MICROKLEAR 418: MicroPowders, Inc.) and 12.77 parts of ion-exchanged water was uniformly dispersed in the paper over-coating composition to prepare a paper over-coating composition of example 8.
(example 9)
A uniformly dispersed paper overcoat composition of example 9 was prepared in the same procedure as in example 8, except that 1.2 parts of polyethylene wax (MPP-635 VF: MicroPowders, Inc.) was added in place of the carnauba wax of example 8.
(example 10)
A uniformly dispersed paper overcoat composition of example 10 was prepared in the same procedure as in example 8, except that 1.2 parts of paraffin wax (MP-28C: MicroPowders, Inc.) was added in place of the carnauba wax of example 8.
Comparative example 1
An overcoat composition for paper was prepared in the same manner as in example 1 except that 85 parts of a commercially available acrylic emulsion C was used in place of the acrylic emulsion (resin 1) in example 1.
The commercially available acrylic emulsion C had a minimum film-forming temperature of 101 ℃, a glass transition temperature of 99 ℃ and an acid value of 49mgKOH/g as a solid content.
Each of the paper overcoat compositions prepared in examples 1 to 10 and comparative example 1 was applied to a weight per unit area of 40g/m using a wire bar2Pure white paper (manufactured by Nippon paper-making Co., Ltd.)) The thickness of the film is 10g/m2The coated paper was dried at 150 ℃ for 20 seconds using a dryer, and the coated paper for evaluation was prepared.
(evaluation of oil resistance)
The salad oil was collected into a dropper, and 0.1ml was dropped onto a test piece of coated paper for evaluation.
After dropping the salad oil, the surface and the back were visually evaluated according to the following evaluation criteria by wiping the salad oil at 60 ℃ for 2 hours and at 120 ℃ for 2 hours.
O: there was no trace of dripping on the surface and no penetration to the back.
And (delta): the surface was marked by dripping, but there was no penetration into the back surface.
X: the surface had traces of dripping, and the liquid penetrated into the back surface.
(evaluation of Water resistance)
Tap water was collected in a dropper, and 0.1ml was dropped on a test piece of coated paper for evaluation.
After dropping tap water, the temperature was measured at 25 ℃ for 30 minutes, and then the tap water was wiped off, and the visual evaluation was performed according to the following evaluation criteria.
O: the surface had no drop marks, no swelling due to water, and no penetration into the back surface.
And (delta): the surface was marked by dripping, but there was no penetration into the back surface.
X: the surface had traces of dripping, swelling due to water, and penetration into the back surface.
(oil repellency evaluation)
The coated paper thus prepared was evaluated for oil repellency using a JAPAN TAPPI pulp test kit No. 41. In the evaluation, the case where the oil repellency was 5 or more was regarded as pass, and the case where the oil repellency was less than 4 was regarded as fail. Oil repellency 12 is maximum and most preferred.
(blocking resistance)
The coated surface of the coated paper thus produced was overlapped so as to be in contact with the coated surface, and 10kgf/cm was applied2The load of (2) was taken out after a lapse of 48 hours at 40 ℃ and the following conditions were appliedThe adhesion of the coated side to the uncoated side was visually evaluated in 4 stages.
(evaluation criteria)
Very good: no blocking was observed at all.
O: some blocking was observed in part.
And (delta): blocking was partially observed.
X: blocking was observed over the entire face.
(sliding angle)
The coated surface of the produced coated paper was overlapped so as to be in contact with the coated surface, and the inclination angle at which the coated paper started to slide was measured as a slide angle by an inclination method. The slide angle was measured using a slide angle inclination measuring device (manufactured by HEIDON corporation).
The same procedure was carried out, and the coated surface of the produced coated paper was overlapped so as to be in contact with the uncoated surface (inside surface), and the slip angle was measured.
Since the smaller the value of the sliding angle, the higher the sliding property, the easier the operation of taking out the coated papers one by one from the coated papers in a laminated state becomes, and the workability improves.
The compositions of the paper overcoat compositions of examples 1 to 10 and comparative example 1 and the evaluation results of the coated paper using the coating compositions are shown in tables 1 and 2.
[ TABLE 1 ]
Figure BDA0003266171320000211
[ TABLE 2 ]
Figure BDA0003266171320000221
The coated paper using the paper top coating composition of the present invention was excellent in water resistance, oil resistance and oil repellency.
In addition, in examples 5 to 8 in which resins having different glass transition temperatures were used in combination, improvement in blocking property and reduction in sliding angle were observed, and in examples 8 to 10 in which wax was added, a further reduction in sliding angle was observed.
[ production of paper laminate [ I ]
(example 11)
Using the paper overcoat composition prepared in example 1 as adhesive S, the coating amount was 3.0g/m by a bar coater2Coated on Paper for straw (Paper Techn., Ltd.; basis weight: 90g/m), dried at 80 ℃ for 1 minute, then 2 pieces of Paper for straw were bonded, and then coated again with a bar coater at a coating weight of 3.0g/m2The resulting laminate was coated on one side of the laminate, dried at 80 ℃ for 1 minute to obtain a paper laminate to which 3 pieces of straw base paper were bonded, and further aged at 40 ℃ for 24 hours.
(examples 12 and 13 and comparative example 2)
The paper top coating compositions prepared in examples 2 and 3 and comparative example 1 were used as adhesives T, U and V, respectively, and 3 pieces of straw base paper were laminated in the same order as in example 11 to prepare a paper laminate, and similarly, aging (aging) was carried out at 40 ℃ for 24 hours.
[ production of paper/film laminate [ II ]
(example 14)
The paper overcoat composition prepared in example 1 was used as an adhesive S, and the coating amount was 3.0g/m by a bar coater2The resin composition was applied to a corona-treated surface of a PET film (film thickness: 12 μm), dried at 80 ℃ for 1 minute, attached to a cup base paper (manufactured by Japan paper-making Co., Ltd.), and then aged at 40 ℃ for 3 days.
(examples 15 and 16 and comparative example 3)
Using the paper topcoat compositions prepared in preparation examples 2 and 3 and comparative example 1 as adhesives T, U and V, respectively, a PET film (film thickness: 12 μm) was laminated to a cupped base paper in the same procedure as in example 14, and then similarly cured (aged) at 40 ℃ for 3 days.
[ evaluation ]
The laminates of examples 11 to 16 and comparative examples 2 to 3 were evaluated as follows, and the results are summarized in tables 3 and 4.
(Water resistance 1: paper laminate [ I ] and paper/film laminate [ II ])
The paper laminate [ I ] and the paper/film laminate [ II ] thus produced were each cut into a strip shape having a width of 15mm, and the strip shape was immersed in tap water at 25 ℃ for 6 hours, and then the state of the laminate was visually evaluated in the following 3 stages.
O: no change in appearance was observed.
And (delta): slight peeling was observed between papers or between papers/films.
X: peeling between sheets, or between sheets/films was observed.
(Water resistance 2: paper laminate [ I ])
The wet tensile strength of the paper substrate was measured according to JIS P8135 for the paper laminate [ I ] thus produced, and the water resistance was evaluated.
O: is 2.0kN/m or more.
And (delta): 1.5 or more and less than 2.0 kN/m.
X: less than 1.5 kN/m.
(sealing Property: paper/film laminate [ II ])
A transparent adhesive tape (TF-12 manufactured by nicoiban corporation) was pressure-bonded to the film surface of the produced paper/film laminate [ II ], and the degree of film peeling when the adhesive tape was peeled off at once was visually evaluated in the following 3 stages.
O: no change in appearance was observed.
And (delta): floating was observed in a part of the film.
X: the film was peeled from the paper.
The evaluation results of the laminates of examples 11 to 16 and comparative examples 2 and 3 are shown in tables 3 and 4.
[ TABLE 3 ]
Figure BDA0003266171320000241
[ TABLE 4 ]
Figure BDA0003266171320000251
The paper laminate of the present invention has excellent water resistance and excellent adhesion.

Claims (13)

1. A composition for paper overcoating and adhesive, characterized by comprising an emulsion containing a resin comprising a styrene-acrylic copolymer of styrene, alpha-methylstyrene and a (meth) acrylic ester, and an aqueous medium, wherein the emulsion has a minimum film-forming temperature in the range of-30 ℃ to 30 ℃.
2. The composition for paper overcoating and adhesive according to claim 1, wherein the emulsion has a glass transition temperature in the range of-40 ℃ to 30 ℃ and an acid value in the range of 30mgKOH/g to 80 mgKOH/g.
3. The composition for paper overcoating and adhesive according to claim 1 or 2, further comprising a copolymer of (meth) acrylic acid and a (meth) acrylic acid ester.
4. The composition for paper overcoating and adhesive according to claim 3, wherein the styrene, the styrene-acrylic copolymer of α -methylstyrene and (meth) acrylic acid ester, and the copolymer of (meth) acrylic acid and (meth) acrylic acid ester form a core-shell structure.
5. The composition for paper overcoating and adhesive according to any one of claims 2 to 4, further comprising a resin having a glass transition temperature higher than that of the resin.
6. The composition for paper overcoating and adhesive agent according to any one of claims 1 to 5, wherein the composition further contains a wax.
7. A coated paper comprising a resin layer of the paper topcoat and adhesive composition according to any one of claims 1 to 6 on a paper substrate.
8. A water and oil resistant paper comprising a resin layer of the paper coating composition and the adhesive composition according to any one of claims 1 to 6 on a paper substrate.
9. A laminate comprising a paper base and a paper base or a plastic film bonded to each other at least,
a resin layer comprising the paper topcoat and adhesive composition according to any one of claims 1 to 6 on at least one side of a paper substrate.
10. The laminate according to claim 9, wherein the paper substrate and the paper substrate or the plastic film are bonded through the resin layer.
11. The laminate according to claim 9 or 10, wherein the resin layer is provided in a portion where the paper substrate and the paper substrate or the plastic film are not laminated.
12. A drinking straw using the laminate according to any one of claims 9 to 11.
13. A tableware using the laminate as claimed in any one of claims 9 to 11.
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